上海夏季PM2.5中有机物的组分特征、空间分布和来源

有机物是大气细颗粒物(PM_(2.5))的重要组成部分,其来源和组分非常复杂,是大气科学研究的难点和热点.本研究定量表征了上海地区夏季3个不同功能站点PM_(2.5)中78种有机组分,分析了其组成特征及空间差异,并采用后向轨迹、指示物、特征比值等方法对其来源进行了探讨.结果表明,上海西部郊区青浦和徐汇的有机组分检出浓度相近,约为(317±129)ng·m~(-3),高于东部沿海.78种有机组分中,脂肪酸类物质的占比最高,之后依次为左旋葡聚糖、正构烷烃和多环芳烃,藿烷的占比最低.基于示踪物比值法初步分析结果表明,上海地区的颗粒有机物主要来源于汽油车尾气排放,此外中心城区和西部郊区在观测期间受到了一定程度的生物质燃烧污染,可能与西北方向的污染输送有关.就具体组分而言,在西部郊区青浦,脂肪酸主要来自于陆生植物排放,而在东部沿海地区临港,其还会受到海洋浮游植物和微生物的影响;PAH特征比值的分析表明煤燃烧和机动车尾气对多环芳烃具有重要贡献.相关研究结果有助于对上海有机气溶胶的污染特征及来源的深入认识,为开展颗粒有机物的防治提供一定的基础支撑.     

不同粒径大气颗粒物中多环芳烃的含量及分布特征

采集了北京城乡结合部与郊区2003年4个季节的不同粒径大气颗粒物样品 ,运用GC/MS分析了其多环芳烃组成 .结果表明 ,17种PAHs总量为 0.84～15.223ng/m³,城乡结合部含量是郊区的1.07～6.60倍 .PAHs总量的季节性变化表现为冬季>秋季>春季>夏季,且随颗粒物粒径减小,含量逐渐增大,大约有68.4%～84.7%的PAHs吸附在≤2.0μm颗粒上.2～3环PAHs呈双峰型分布,4～6环PAHs呈单峰型分布 ,PAHs分子量越大 ,MMD值越小 ,燃煤取暖与低温是导致冬季PAHs污染增高的主要因素.     

北京部分地区大气PM10中多环芳烃的季节性变化

采集了北京城乡结合部和郊区 2003 年 4 个季节大气 PM10样品,用超声萃取-GC/MS 技术分析了其多环芳烃的组成.结果表明,17 种母核多环芳烃总量在8.46~296.57ng/m3之间,城乡结合部的浓度是郊区的1.02~1.58倍.PAHs总量的季节性变化与采样时环境温度显示出较好的负相关性,即冬季>秋季>春季>夏季.郊区和城乡结合部冬季 PAHs 总量分别是夏季的 22.25 倍和 34.41 倍,显示了燃煤取暖对北京冬季大气 PAHs 污染的贡献极为显著.运用多种多环芳烃比值综合判断,北京大气 PM10中 PAHs 主要以燃煤和机动车尾气混合来源为主,石油源和木材燃烧源的贡献较小.     

广州秋季不同功能区大气颗粒物中PAHs粒径分布

利用MOUDI^TM级联分段式采样器采集了秋季广州市区(荔湾采样点和五山采样点)及郊区(新垦采样点)3个采样点的气溶胶样品并使用GC-MS分析了样品中13种多环芳烃的含量.发现3～4环的多环芳烃呈双峰分布,5～7环的多环芳烃呈单峰分布.广州市区和郊区的多环芳烃具有不同粒径分布模式;相对于城区,郊区的多环芳烃存在于更大的颗粒物中,这可能是气溶胶的陈化过程不同导致的.城区的多环芳烃可能主要受吸附作用控制,而郊区的多环芳烃则可能受多种机制控制,如吸附作用、吸收作用和多层吸附.诊断参数值在粒径1～2.5μm和0.1～0.56μm存在较大差异;从浓度上看新垦13种多环芳烃的总浓度为39ng/m³,五山为71～94ng/m³,荔湾为32～154 ng/m³;从组成上看广州市大气颗粒物种多环芳烃以5～7环为主.     

太原市空气颗粒物中正构烷烃分布特征及来源解析

为明确城市空气颗粒物中正构烷烃分布特征及污染来源,采集采暖和非采暖季环境空气PM10样品和典型排放源(高等植物、燃煤和机动车)样品,利用GC-MS测定正构烷烃,选取诊断参数并结合污染源排放特征讨论PM10中正构烷烃分布和来源,采用主成分分析法定量解析源贡献率.结果表明,环境空气PM10中正构烷烃含量呈较强时空变化,采暖和非采暖季浓度分别为213.74~573.32 ng·m-3和22.69~150.82 ng·m-3,前者总浓度最高是后者的18倍;采暖季郊区点位(JY、JCP、XD和SL)浓度均高于市区,以JY最高(577.32 ng·m-3),非采暖季工业区(JS)总烷烃量(150.82 ng·m-3)明显高于其它点位,是SL总量的7倍.采暖季化石燃料来源烷烃(C n≤C24)与总烷烃量相关性优于植物来源烷烃(C n≥C25),非采暖季相反,表明前者化石燃料输入较后者高.CPI和%WNA指示非采暖季植物贡献率较采暖季高,且植物蜡烷烃随环境压力的增大总产率增加;C max和OEP表明非采暖季PM10中有机质成熟度低于采暖季;两季样品TIC图均存在UCM鼓包,机动车尾气是该城市的重要污染源.PCA解析结果表明太原市环境空气PM10中正构烷烃首要排放源为机动车尾气和高等植物,约占51.28%;其次为煤烟尘,贡献率为43.14%.煤烟尘污染控制协同机动车尾气净化措施的完善将成为降低城市空气颗粒物中正构烷烃浓度的有效途径.     

应用自动识别与定量分析数据库筛查黄河和长江水中有机污染物

采用气质联用分析,并应用自动识别与定量分析数据库(AIQS-DB)对黄河下游和长江下游水样中近1000种有机污染物进行了筛查.结果表明,黄河下游山东段和长江下游江苏段水样分别检出95种和121种化合物,主要包括正构烷烃、多环芳烃、酚类、硝基化合物、酞酸酯类、农药和药物等.其中,黄河和长江水样中正构烷烃平均浓度分别为1806ng/L和720ng/L;16种优控PAHs平均浓度分别为27ng/L和30ng/L;6种优控PAEs的平均浓度分别为77ng/L和2166ng/L;黄河和长江水样分别检出9种和17种农药.黄河各采样点间污染物浓度差别较大,而长江采样点间浓度相差较小.研究表明,气质联用结合AIQS-DB可有效用于区域性污染物的筛查.     

Seasonal variation and source apportionment of organic and inorganic compounds in PM2.5 and PM10 particulates in Beijing, China

The distribution and source of the solvent-extractable organic and inorganic components in PM 2.5(aerodynamics equivalent diameter below 2.5 microns),and PM 10(aerodynamics equivalent diameter below 10 microns) fractions of airborne particles were studied weekly from September 2006 to August 2007 in Beijing.The extracted organic and inorganic compounds identified in both particle size ranges consisted of n-alkanes,PAHs(polycyclic aromatic hydrocarbons),fatty acids and water soluble ions.The potential emission sources of these organic compounds were reconciled by combining the values of n-alkane carbon preference index(CPI),%waxC n,selected diagnostic ratios of PAHs and principal component analysis in both size ranges.The mean cumulative concentrations of n-alkanes reached 1128.65ng/m3 in Beijing,74% of which(i.e.,831.7ng/m3) was in the PM 2.5 fraction,PAHs reached 136.45ng/m3(113.44ng/m3 or 83% in PM 2.5),and fatty acids reached 436.99ng/m3(324.41ng/m3 or 74% in PM 2.5),which resulted in overall enrichment in the fine particles.The average concentrations of SO42-,NO3-,and NH4+ were 21.3±15.2,6.1±1.8,12.5±6.1μg/m3 in PM 2.5,and 25.8±15.5,8.9±2.6,16.9±9.5μg/m3 in PM 10,respectively.These three secondary ions primarily existed as ammonium sulfate((NH4)2SO4),ammonium bisulfate(NH4HSO4) and ammonium nitrate(NH4NO3).The characteristic ratios of PAHs revealed that the primary sources of PAHs were coal combustion,followed by gasoline combustion.The ratios of stearic/palmitic acid indicated the major contribution of vehicle emissions to fatty acids in airborne particles.The major alkane sources were biogenic sources and fossil fuel combustion.The major sources of PAHs were vehicular emission and coal combustion.     

哈尔滨市大气气相中多环芳烃的研究

在哈尔滨地区8个采样点同时安装了PUF大气被动采样器,研究了该地区2007年春季(1月末~4月末)大气气相中多环芳烃的含量和分布特征.结果表明,PUF大气被动采样器主要采集了大气气相中三环和四环的多环芳烃,占总量的91.22%~96.37%,PAHs的浓度具有明显的功能区差异,依次为:市区(356.49 ng/d),郊区(162.65 ng/d),农村(278.35 ng/d),偏远地区(183.99 ng/d),市区大气中多环芳烃的浓度是农村的2倍,偏远地区的3倍.污染源是影响大气中多环芳烃含量高低的主要因素,通过特征分子含量比值法对该地区大气中多环芳烃的来源进行了初步研究,结果表明,哈尔滨地区城市大气中多环芳烃主要来自于燃煤,农村大气中的多环芳烃主要来自于农作物秸秆的燃烧.利用毒性当量因子法对该地区大气气相中多环芳烃的健康风险进行了评价,具有与浓度分布类似的功能区差异,表明市区和农村地区大气中PAHs对于人们的健康存在较大潜在威胁.通过安装平行采样器,PUF被动采样器具有很好的重现性,研究表明,可以用于城市尺度多个采样点大气中多环芳烃的同时研究.     

餐饮源有机颗粒物排放特征

餐饮油烟是大气有机颗粒物的重要来源之一.本研究在深圳市内选择了西餐、茶餐厅、职工食堂和韩式料理这4种类型的餐馆,通过对这4类餐厅的外场采样,分析各类型餐厅油烟中有机颗粒物的化学组成,筛选了餐饮油烟污染源的有机特征组分.结果表明,各餐馆排放的PM_(2.5)中,有机物占60%以上.在所有定量的有机组分之中,脂肪酸含量最高,其次是二元羧酸和正构烷烃,而多环芳烃、甾醇和单糖等有机组分的含量较低.颗粒物的有机组成特征受到菜系的影响,西餐厅和韩式料理排放脂肪酸、正构烷烃和多环芳烃等有机物含量较高,但却排放了低含量的甾醇和单糖,茶餐厅和职工食堂则相反.餐饮源颗粒物中Fla/(Fla+Pyr)和LG/(Gal+Man)的比值受菜系影响较小,也区别于其他污染源的特征比值,可以作为餐饮源潜在的示踪物.餐饮源为深圳市大气颗粒物贡献了大量的脂肪酸和二元羧酸.     

Distribution and sources of solvent extractable organic compounds in PM2:5 during 2007 Chinese Spring Festival in Beijing

The solvent extractable organic compounds (SEOC), including n-alkanes, polycylic aromatic hydrocarbons, fatty acids, anddicarboxylic acids in PM2.5 during the 2007 Chinese Spring Festival in Beijing, were measured via gas chromatography-massspectrometry for determining the characteristics and sources of these organic pollutants. The concentrations of total n-alkanes, PAHs,and organic acids before Chinese Spring Festival Eve (1025.5, 95.9, and 543.3 ng/m3, respectively) were higher than those after (536.6,58...     

Compositions and sources of organic acids in fine particles (PM2.5) over the Pearl River Delta region, south China

Organic acids as important constituents of organic aerosols not only influence the aerosols' hygroscopic property, but also enhance the formation of new particles and secondary organic aerosols. This study reported organic acids including C14–C32fatty acids, C4–C9dicarboxylic acids and aromatic acids in PM2.5collected during winter 2009 at six typical urban, suburban and rural sites in the Pearl River Delta region. Averaged concentrations of C14–C32fatty acids, aromatic acids and C4– C9 dicarboxylic acids were 157, 72.5 and 50.7 ng/m3, respectively. They totally accounted for 1.7% of measured organic carbon. C20–C32fatty acids mainly deriving from higher plant wax showed the highest concentration at the upwind rural site with more vegetation around, while C14–C18fatty acids were more abundant at urban and suburban sites, and dicarboxylic acids and aromatic acids except 1,4-phthalic acid peaked at the downwind rural site. Succinic and azelaic acid were the most abundant among C4–C9dicarboxylic acids, and 1,2-phthalic and 1,4-phthalic acid were dominant aromatic acids. Dicarboxylic acids and aromatic acids exhibited significant mutual correlations except for 1,4-phthalic acid, which was probably primarily emitted from combustion of solid wastes containing polyethylene terephthalate plastics. Spatial patterns and correlations with typical source tracers suggested that C14–C32fatty acids were mainly primary while dicarboxylic and aromatic acids were largely secondary. Principal component analysis resolved six sources including biomass burning, natural higher plant wax, two mixed anthropogenic and two secondary sources; further multiple linear regression revealed their contributions to individual organic acids. It turned out that more than 70% of C14–C18fatty acids were attributed to anthropogenic sources, about 50%–85% of the C20–C32fatty acids were attributed to natural sources, 80%–95% of dicarboxylic acids and 1,2-phthalic acid were secondary in contrast with that 81% of 1,4-phthalic acid was primary.     

乌鲁木齐市典型城区大气PAHs气-粒分配特征

大气中PAHs的气-粒分配是影响其在大气中分布、迁移和转化的一个重要因素,于2011年12月—2012年12月在乌鲁木齐市天山区采集大气气相和颗粒相样品,对聚氨酯泡沫样品的气相和石英纤维膜的颗粒相(TSP)中的16种PAHs进行分析.结果表明:采样期间颗粒相和气相中ρ(∑₁₆PAHs)总和的年均值为(116.71±92.74) ng/m3,采暖期〔(173.16±84.26) ng/m3〕是非采暖期〔(39.46±16.19) ng/m3〕的4.4倍;采暖期颗粒相中ρ(∑₁₆PAHs)平均值为(40.60±3.03) ng/m3,气相为(134.46±13.05) ng/m3,2～3环PAHs主要存在于在气相中,4～6环PAHs主要存在于颗粒相中.在非采暖期,颗粒相ρ(∑₁₆PAHs)平均值为(25.37±3.21) ng/m3,气相为(14.95±1.06) ng/m3.采用吸附和吸收模型对PAHs的分配特征进行了研究,表明PAHs的lg K_p(K_p为分配系数)与lg P_L0(P_L0为过冷蒸汽压)线性关系显著,在采暖期斜率绝对值为0.34,说明PAHs的气-粒分配以吸收为主;在非采暖期的斜率绝对值为0.78,表明PAHs的气-粒分配受吸收和吸附共同作用.PAHs的lg K_p与lg K_oa(K_oa为正辛醇-大气分配系数)线性关系显著,在采暖期斜率为0.38,表明PAHs气-粒分配并未达到平衡;在非采暖期,斜率为1.22,表明PAHs气-粒分配接近平衡.研究显示,乌鲁木齐市城区大气PAHs气-粒分配在采暖期及非采暖期特征不同,应区别制订政策和管理措施.      

Mercury in leaf litter in typical suburban and urban broadleaf forests in China

Leaf litterfall plays an important role in transporting atmospheric mercury to soil in forests area.     

2016年夏季南京大气污染特征观测分析

为研究南京夏季大气复合污染的特征,2016年8月15日~9月15日期间开展了强化观测实验,本文利用仙林、鼓楼80m楼顶2个站点的强化观测资料,结合草场门常规监测资料,统计分析了南京不同地区夏季O₃和颗粒物（PM_2.5、PM₁₀）的浓度特征和相关性,以及郊区水溶性离子与其气态前体物的转化率变化特征.研究表明：3个站点O₃平均小时浓度为100.3μg/m³.PM_2.5和PM₁₀浓度分别为41.1和67.8μg/m³,郊区夜间存在颗粒物浓度高值.SO₄^2-、NO₃^-、NH₄⁺浓度总和占PM_2.5浓度的比值达到61%,OC（有机碳）/EC（元素碳）比值范围为0.8~4.0,日均值超过2.0的天数占77%,城、郊均存在二次污染.白天O₃与颗粒物（PM_2.5）浓度呈显著正相关变化,硫转化率（SOR）、氮转化率（NOR）分别与O₃浓度、湿度显著正相关.HONO主要在夜间积累,HCl和HNO₃浓度峰值出现在下午.与其它无机盐相比,NH₄⁺在总氨中所占比例明显偏低,大气中的氨主要以气态NH₃存在.观测期间O₃污染较重,O₃与颗粒物的正相关关系显著,化学反应在颗粒物积累过程中具有重要贡献,此外还可能存在城区向郊区的污染输送.     

渤海湾潮滩不同粒径沉积物中多环芳烃的分布

利用湿筛分离的方法,将采自渤海湾潮间带的沉积物分成0.063mm 3个不同的粒径组分,测定其16种EPA规定的多环芳烃(PAHs)含量、总有机碳(TOC)和碳黑(BC)含量.结果表明,不同粒径沉积物中∑PAHs含量范围在714~4870ng/g之间.在岐口(TS3)沉积物中,∑PAHs含量最高值出现在0.063mm粒径组分中.所有站点沉积物的0.031~0.063mm粒径组分中∑PAHs含量均为最低.尽管如此,有机碳标准化∑PAHs含量则随着沉积物粒径的增大呈现增加趋势.不同粒径沉积物中∑PAHs含量与BC含量之间呈现显著正相关关系,而与有机碳(OC=TOC-BC)含量之间的相关性较差.因此,不同粒径沉积物中BC的分布很可能在其中扮演着更重要的作用.     

淮河中下游沉积物PAHs的稳定碳同位素源解析

对淮河中下游水相、悬浮物、沉积物中的PAHs(多环芳烃)进行定量分析,在探讨其分布特征的基础上,利用单体烃稳定碳同位素技术揭示研究区沉积物中PAHs的来源. 结果表明:水相中正阳关的ρ(PAHs)最高,达5.01 ng/mL;悬浮物和沉积物中以蚌埠闸的w(PAHs)最高,分别为9.85和1 175.02 ng/g. 沉积物中PAHs的δ13C在-39.4‰~-17.6‰之间.正阳关、平圩、洛河和蚌埠闸等采样点的高环PAHs的δ13C比低环PAHs的小,表明高环PAHs富集12C（轻碳同位素）,显示燃煤源为主要污染源;但这4个采样点PAHs的δ13C与燃煤烟尘相比存在一定差异,表明除燃煤源外可能还存在着少量其他污染源. 双沟镇高环PAHs的δ13C比低环PAHs的大,表明高环PAHs富集13C（重碳同位素),可能是微生物作用所致.      

北京市大气颗粒物中多环芳烃(PAHs)污染特征

对北京市2003-09～2004-07的10个月空气中的TSP样品进行了连续采样,周期为1次/周.分析了15种3～7环的PAHs,其中以4～5环为主.∑PAHs浓度及BaP的最大值分别达到705 ng/m³和52 ng/m³;春夏秋冬4季∑PAHs的平均浓度分别为46 ng/m³,16 ng/m³,52 ng/m³,268 ng/m³;BaP的4季平均浓度分别为2.8ng/m³,0.23 ng/m³,3.3 ng/m³,16ng/m³;采暖期∑PAHs平均浓度为非采暖期的9.5倍.在所分析的3种气象条件中,降水能够明显降低PAHs的浓度;非采暖期的PAHs浓度随温度的升高而降低,采暖期的浓度与温度没有明显的相关性;采暖期风速水平的增加会导致PAHs浓度的下降,而非采暖期不同环数的PAHs和风速水平的关系各异,3环的PAHs浓度随风速水平增加而增加,4、5环的PAHs浓度变化不大,6、7环PAHs随风速水平的增加而浓度下降.     

Primary and secondary organic aerosol in an urban/industrial site: Sources, health implications and the role of plastic enriched waste burning

PM10 samples were collected from an urban/industrial site nearby Athens, where uncontrolled burning activities occur. PAHs, monocarboxylic, dicarboxylic, hydroxycarboxylic and aromatic acids, tracers from BVOC oxidation, biomass burning tracers and bisphenol A were determined. PAH, monocarboxylic acids, biomass burning tracers and bisphenol A were increased during autumn/winter, while BSOA tracers, dicarboxylic- and hydroxycarboxylic acids during summer. Regarding aromatic acids, different sources and formation mechanisms were indicated as benzoic, phthalic and trimellitic acids were peaked during summer whereas p-toluic, isophthalic and terephthalic were more abundant during autumn/winter. The Benzo[a]pyrene-equivalent carcinogenic power, carcinogenic and mutagenic activities were calculated showing significant (p < 0.05) increases during the colder months. Palmitic, succinic and malic acids were the most abundant monocarboxylic, dicarboxylic and hydrocarboxylic acids during the entire sampling period. Isoprene oxidation was the most significant contributor to BSOA as the isoprene-SOA compounds were two times more abundant than the pinene-SOA (13.4 ± 12.3 and 6.1 ± 2.9 ng/m³, respectively). Ozone has significant impact on the formation of many studied compounds showing significant correlations with: isoprene-SOA (r = 0.77), hydrocarboxylic acids (r = 0.69), pinene-SOA (r = 0.63),dicarboxylic acids (r = 0.58), and the sum of phthalic, benzoic and trimellitic acids (r = 0.44). PCA demonstrated five factors that could explain sources including plastic enriched waste burning (30.8%), oxidation of unsaturated fatty acids (23.0%), vehicle missions and cooking (9.2%), biomass burning (7.7%) and oxidation of VOCs (5.8%). The results highlight the significant contribution of plastic waste uncontrolled burning to the overall air quality degradation.     

Progressively narrow the gap of PM2.5 pollution characteristics at urban and suburban sites in a megacity of Sichuan Basin, China

Nowadays, the fine particle pollution is still severe in some megacities of China, especially in the Sichuan Basin, southwestern China. In order to understand the causes, sources, and impacts of fine particles, we collected PM_2.5 samples and analyzed their chemical composition in typical months from July 2018 to May 2019 at an urban and a suburban (background) site of Chengdu, a megacity in this region. The daily average concentrations of PM_2.5 ranged from 5.6-102.3 µg/m³ and 4.3-110.4 µg/m³ at each site. Secondary inorganics and organic matters were the major components in PM_2.5 at both sites. The proportion of nitrate in PM_2.5 has exceeded sulfate and become the primary inorganic component. SO₂ was easier to transform into sulfate in urban areas because of Mn-catalytic heterogeneous reactions. In contrast, NO₂ was easily converted in suburbs with high aerosol water content. Furthermore, organic carbon in urban was much greater than that in rural, other than elemental carbon. Element Cr and As were the key cancer risk drivers. The main sources of PM_2.5 in urban and suburban areas were all secondary aerosols (42.9%, 32.1%), combustion (16.0%, 25.2%) and vehicle emission (15.2%, 19.2%). From clean period to pollution period, the contributions from combustion and secondary aerosols increased markedly. In addition to tightening vehicle controls, urban areas need to restrict emissions from steel smelters, and suburbs need to minimize coal and biomass combustion in autumn and winter.     

东海大气气溶胶中二元羧酸的分布特征及来源

大气气溶胶中的二元羧酸因其在全球气候变化中的潜在作用而受到广泛关注.利用2011年5月12日-6月6日在东海采集的气溶胶样品,分析其中水溶性二元羧酸及常量离子浓度,探讨东海气溶胶中二元羧酸的时空分布特征及来源.结果显示东海大气气溶胶中乙二酸、丙二酸和丁二酸的浓度分别为26.0～1475.5 ng·m-3、0.1 ～61.4 ng·m-3和0.1～132.4 ng·m-3,乙二酸在这3种二元羧酸中的贡献最大,为88.3％.东海气溶胶中二元羧酸浓度的昼夜变化不显著.空间分布整体呈现近海高、远海低的趋势.气团的来源和迁移路径以及气象因素影响气溶胶中二元羧酸的分布,气团来自污染较重的陆源时气溶胶中二元羧酸的浓度较高,气团来自清洁的海洋源时,二元羧酸的浓度则较低;阴雾天气时气溶胶中二元羧酸浓度相对较高,降雨发生时二元羧酸的浓度较低.二元羧酸与常量离子的相关性分析表明,自然源和人为源释放的挥发性有机物质在液相中氧化生成二元羧酸是东海大气气溶胶中二元羧酸的主要源,而汽车尾气和生物质燃烧的一次排放、海洋源以及碱性粗颗粒吸收气体二元羧酸不是主要源.液相中乙醛酸氧化形成的乙二酸和长链二元羧酸氧化形成的乙二酸对东海气溶胶中乙二酸的贡献分别为41％和59％.